EP4326678A1 - Non-spherical primary silica nanoparticles and the use therefor - Google Patents

Non-spherical primary silica nanoparticles and the use therefor

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Publication number
EP4326678A1
EP4326678A1 EP22792670.6A EP22792670A EP4326678A1 EP 4326678 A1 EP4326678 A1 EP 4326678A1 EP 22792670 A EP22792670 A EP 22792670A EP 4326678 A1 EP4326678 A1 EP 4326678A1
Authority
EP
European Patent Office
Prior art keywords
water
organoalkoxysilanes
silica nanoparticles
mixture
spherical primary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22792670.6A
Other languages
German (de)
English (en)
French (fr)
Inventor
Gerhard Jonschker
Rene Lutz
Christos KYRIAKOU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Versum Materials US LLC
Original Assignee
Versum Materials US LLC
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Filing date
Publication date
Application filed by Versum Materials US LLC filed Critical Versum Materials US LLC
Publication of EP4326678A1 publication Critical patent/EP4326678A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • the present disclosure relates to the production of non-spherical primary silica nanoparticles for use as an abrasive in CMP compositions.
  • CMP chemical mechanical polishing
  • CMP is employed to planarize metal and/or oxide surfaces.
  • CMP utilizes the interplay of chemical and mechanical action to achieve the planarity of the to-be-polished surfaces.
  • Chemical action is provided by a chemical composition, also referred to as CMP composition or CMP slurry.
  • Mechanical action is usually carried out by a polishing pad which is typically pressed onto the to-be-polished surface and mounted on a moving platen. The movement of the platen is usually linear, rotational or orbital.
  • a rotating wafer holder brings the to-be-polished wafer in contact with a polishing pad.
  • the CMP composition is usually applied between the to-be-polished wafer and the polishing pad.
  • CMP abrasives has substantial influence on their performance in the planarization process. Recently, it was found that non-spherically shaped particles can show higher removal rates and higher efficiency than round shaped particles, so research has focused on providing methods to produce non-spherically shaped particles in a reproducible manner.
  • these particles are made by a controlled aggregation process, in which the colloidal particle formation in at least one phase of the production is deliberately driven to an instable region so that the intermediately formed spherical nanoparticles start to agglomerate. Then, the particles are brought back to a stable region when the desired size and structure is formed.
  • a controlled aggregation process in which the colloidal particle formation in at least one phase of the production is deliberately driven to an instable region so that the intermediately formed spherical nanoparticles start to agglomerate. Then, the particles are brought back to a stable region when the desired size and structure is formed.
  • the present invention satisfies this need by providing non-spherical primary silica nanoparticles and use the non-spherical primary silica nanoparticles as the abrasive in CMP process.
  • a process of synthesizing non-spherical primary silica nanoparticles, or non-spherical primary silica nanoparticles dispersion comprising: a) providing a first mixture containing at least two organoalkoxysilanes and each having a structure of Formula I: wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of OR or R, wherein R is a substituted or unsubstituted linear or branched C1-C12 alkyl group, a C 3 -C 8 cycloaliphatic group, a C 2 -C 6 alkylene group, a halogen, or an aryl group; and at least two, preferably at least three of R 1 , R 2 , R 3 , and R 4 are OR; wherein at least one of the at least two organoalkoxysilanes has at least three of, preferably all R 1 ,
  • Step d) can be performed by (1) adding the water-miscible organic solvent into the mixture of at least two organoalkoxysilanes to obtain a first mixture, and adding the alkaline catalyst into the first mixture; (2) adding the alkaline catalyst into the water- miscible organic solvent to obtain a first mixture, and adding the mixture of at least two organoalkoxysilanes into the first mixture; or (3) adding the water-miscible organic solvent into the mixture of at least two organoalkoxysilanes to obtain a first mixture, adding the water-miscible organic solvent into the alkaline catalyst to obtain a second mixture, and mixing the first and the second mixtures in a mixer in a flow reactor. Water can be added in the reaction mixture if there is not enough water in the mixture of a) to c).
  • the at least two organoalkoxysilanes include but are not limited to the group consisting of tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, triethylmethoxysilane, fluorotriisopropoxysilane, fluorotrimeth
  • the first organoalkoxysilane may be present from about 50 to about 99 mole% and the second organoalkoxysilane may be present at from about 50 to about 1 mole%.
  • the first organoalkoxysilane may be present from about 75 to about 95 mole% and the second organoalkoxysilane may be present at from about 5 to about 25 mole%.
  • the first organoalkoxysilane may be present from about 85 to about 90 mole% and the second organoalkoxysilane may be present at from about 15 to about 10 mole%.
  • the mole% is based on the total mole of the two organoalkoxysilanes is 100%.
  • the first mixture, the second mixture and the reaction mixture can be heated and maintained at a temperature from 30 °C to 70 °C, from 40 °C to 60 °C, or from 48 °C to 52 °C.
  • the non-spherical primary silica nanoparticles is produced at a yield of at least 50%, 75% or 85% based on total weight of particles produced in the process.
  • the non-spherical primary silica nanoparticles is produced at a weight % yield 3.0 wt.% - 8.0 wt.%, 4.0 wt.% - 7.0 wt.%, 4.5 wt.% - 6.5 wt.%, 5.5 wt.% - 6.5 wt.% .
  • the weight% yield is based on the total weight of silica nanoparticles which can be produced by the total weight of the reaction mixture.
  • the non-spherical primary silica nanoparticles have shapes selected from the group consisting of elongated, bent, branched, and combinations thereof, and contain a nitrogen level (or nitrogen content ) of ⁇ 0.2, 0.1 , 0.02, 0.01 , 0.006, 0.005, or 0.004 mmol/g S1O2.
  • non-spherical primary silica nanoparticles or non-spherical primary silica nanoparticles dispersion wherein the non-spherical primary silica nanoparticles have shapes selected from the group consisting of elongated, bent, branched, and combinations thereof, and contain a nitrogen level (or nitrogen content) of ⁇ 0.2, 0.1 , 0.02, 0.01 , 0.006, 0.005, or 0.004 mmol/g S1O2.
  • CMP Chemical Mechanical Planarization
  • FIG. 1 is a Scanning Electron Microscopes (SEM) micrograph at 20,000 X of the non-spherical primary silica nanoparticles produced by Example 2;
  • FIG. 2 is a SEM micrograph at 100,000 X of the non-spherical primary silica nanoparticles produced by Example 2;
  • FIG. 3 is a SEM micrograph at 20,000 X of the non-spherical primary silica nanoparticles produced by Example 3;
  • FIG. 4 is a SEM micrograph at 100,000 X of the non-spherical primary silica nanoparticles produced by Example 3;
  • FIG. 5 is a SEM micrograph at 20,000 X of the non-spherical primary silica nanoparticles produced by Example 4.
  • FIG. 6 is a SEM micrograph at 100,000 X of the non-spherical primary silica nanoparticles produced by Example 4.
  • nanoparticle(s) and “colloid(s)” are synonymous and denote particles whose size is between 1 and 1000 nanometers.
  • compositions wherein specific components of the composition are discussed in reference to weight percentage ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.00001 weight percent, based on the total weight of the composition in which such components are employed.
  • non-spherical silica nanoparticles refers to both non-spherical silica primary nanoparticles, and non-spherical silica secondary nanoparticles
  • non-spherical used herein includes all shapes or structures that are not spherical. It includes but not limited to “elongated”, “bent structure” and “branched structure”, and combinations thereof.
  • non-spherical primary silica nanoparticles refers to a primary silica particle having a structure in which the silica grows in a shape of non-linear, elongated, bent, branched, or combinations. More specifically, the term refers to a structure that the silica particles grow inhomogeneously in more than one direction at the same time and thereby producing a non-spherical structure.
  • a spherical primary silica nanoparticle refers to a structure when the silica particle grow homogeneously in all directions and thereby producing a spherical structure.
  • non-spherical primary silica nanoparticles do not include the aggregated particles, or aggregated primary particles, or aggregated spherical primary particles.
  • the present invention provides a process of synthesizing non-spherical primary silica nanoparticles using at least two organoalkoxysilanes at the same time, where the chosen organoalkoxysilanes have different reaction speeds with water under alkaline conditions.
  • the present invention provides a process of synthesizing non- spherical primary silica nanoparticles or non-spherical primary silica nanoparticles dispersion; wherein the process comprises the following steps: a) providing a first mixture of at least two organoalkoxysilanes and each organoalkoxysilane independently has a structure represented by Formula I: wherein
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of OR or R, wherein R is a substituted or unsubstituted linear or branched Ci- Ci2 alkyl group, a C 3 -C 8 cycloaliphatic group, a C 2 -C 6 alkylene group, a halogen, or an aryl group, and at least two, preferably at least three of the R 1 , R 2 , R 3 , and R 4 are OR; wherein at least one of the at least two organoalkoxysilanes having at least three of, preferably all R 1 , R 2 , R 3 , and R 4 as OR; and the at least two organoalkoxysilanes have different reaction speeds with water under alkaline conditions; b) providing a water-miscible organic solvent; c) providing an alkaline catalyst; d) obtaining a reaction mixture comprising a) to c); wherein the reaction mixture contains water and has
  • the pH of the reaction mixture is generally in the range of 7 to 14, preferably 10 to 14, and more preferably 12 to 14.
  • Step d) can be performed by (1 ) adding the water-miscible organic solvent into the mixture of at least two organoalkoxysilanes to obtain a first mixture, and adding the alkaline catalyst into the first mixture; (2) adding the alkaline catalyst into the water- miscible organic solvent to obtain a first mixture, and adding the mixture of at least two organoalkoxysilanes into the first mixture; or (3) adding the water-miscible organic solvent into the mixture of at least two organoalkoxysilanes to obtain a first mixture, adding the water-miscible organic solvent into the alkaline catalyst to obtain a second mixture, and mixing the first and the second mixtures in a mixer in a flow reactor. Water can be added in the reaction mixture if there is not enough water in the mixture of a) to c).
  • the at least two organoalkoxysilanes include but are not limited to the group consisting of tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, triethylmethoxysilane, fluorotriisopropoxysilane, fluorotrimeth
  • the preferred at least two organoalkoxysilanes comprise tetramethoxysilane and tetraethoxysilane.
  • the concentrations (mole%) of the at least two organoalkoxysilanes can be any value.
  • the first organoalkoxysilane may be present from about 50 to about 99 mole% and the second organoalkoxysilane may be present at from about 50 to about 1 mole%.
  • the first organoalkoxysilane may be present from about 75 to about 95 mole% and the second organoalkoxysilane may be present at from about 5 to about 25 mole%.
  • the first organoalkoxysilane may be present from about 85 to about 90 mole% and the second organoalkoxysilane may be present at from about 15 to about 10 mole%.
  • the mole% is based on the total mole of the two organoalkoxysilanes is 100%.
  • the first mixture, the second mixture and the reaction mixture can be heated and maintained at a temperature from 30 °C to 70 °C, from 40 °C to 60 °C, or from 48 °C to 52 °C.
  • the non-spherical primary silica nanoparticles is produced at a yield of at least 50%, 75% or 85% based on total weight of particles produced in the process. That is, 50%, 75% or 85% of the total particles produced in the process are non-spherical primary silica nanoparticles.
  • the non-spherical primary silica nanoparticles is produced at a weight % yield of 3.0 wt.% - 8.0 wt.%, 4.0 wt.% - 7.0 wt.%, 4.5 wt.% - 6.5 wt.%, 5.5 wt.% - 6.5 wt.% .
  • the weight% yield is based on the total weight of silica nanoparticles which can be produced by the total weight of the reaction mixture.
  • the non-spherical primary silica nanoparticles have shapes selected from the group consisting of elongated, bent, branched, and combinations thereof, and contain a nitrogen level (or nitrogen content) of ⁇ 0.2, 0.1 , 0.02, 0.01 , 0.006, 0.005, or 0.004 mmol/g Si0 2 .
  • non-spherical primary nanoparticles do not include the aggregated particles, such as aggregated primary particles.
  • the Stober process is a well-known prior art process for making spherically- shaped silica particles.
  • tetraethyl orthosilicate TEOS
  • the process of the present invention comprises modifications to the Stober process that led to a surprising and unexpected result of non-spherical primary silica nanoparticles.
  • the process of the present invention comprises the step of reacting at least two organoalkoxysilanes with water in a reaction mixture.
  • Each of the at least two organoalkoxysilane independently has a structure represented by Formula I shown below:: wherein
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of OR or R, wherein R is a substituted or unsubstituted linear or branched C1-C12 alkyl group, a C 3 -C 8 cycloaliphatic group, a C 2 -C 6 alkylene group, a halogen, or an aryl group, wherein at least two. preferably at least three of R 1 , R 2 , R 3 , and R 4 is OR.
  • At least one of the at least two organoalkoxysilanes has at least three of, preferably all, R 1 , R 2 , R 3 , and R 4 as OR.
  • organoalkoxysilanes represented by the Formula I include tetramethoxysilane(TMOS), tetraethoxysilane (TEOS), tetraisopropoxysilane, tetrabutoxysilane, tetraoctoxysilane, methyltrimethoxysilane (MTMS), methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, pheny
  • the at least two organoalkoxysilanes should be deliberately selected to have different reaction speeds with water in alkaline conditions.
  • S1O2 seed formation by each organoalkoxysilane starts at different times.
  • the organoalkoxysilane having a faster speed of reaction reacts first with water to form silanols and subsequently S1O2 seeds according to the well-established LaMer theory. While these seeds are beginning to grow, the other organoalkoxysilane having a slower speed of reaction starts producing new silanols which also create subsequently new seeds. Thus, the seed formation and particle growth reactions are taking place at the same time due to the different reaction speeds of the two organoalkoxysilanes with water.
  • a new seed can be growing by itself or a new seed can be attached to a growing seed to form another seed.
  • the process in present invention forms a surprising and unexpected result of non-spherical primary silica nanoparticles.
  • the process is unique because at least two organoalkoxysilanes having different reaction speeds with water under alkaline conditions are used at the same time comparing with the known processes where only one organoalkoxysilane is used, or is used at one time.
  • the first organoalkoxysilane may be present from about 50 to about 99 mole% and the second organoalkoxysilane may be present at from about 50 to about 1 mole%.
  • the first organoalkoxysilane may be present from about 75 to about 95 mole% and the second organoalkoxysilane may be present at from about 5 to about 25 mole%.
  • the first organoalkoxysilane may be present from about 85 to about 90 mole% and the second organoalkoxysilane may be present at from about 15 to about 10 mole%.
  • the mole% is based on the total mole of the two organoalkoxysilanes is 100%.
  • the at least two organoalkoxysilanes are TEOS and TMOS.
  • the TEOS is present from about 75 to about 98 mole% and the TMOS is present from about 2 to about 25 mole%, more preferable the TEOS is present from about 85 to about 95 mole% and the TMOS is present from about 5 to about 15 mole%, and most preferably the TEOS is present from about 88 to about 92.5 mole% and the TMOS is present from about 7.5 to about 12 mole%.
  • the TEOS is present at 90 mole% and the TMOS is present at 10 mole%.
  • Water is a reactant in the process of the present invention.
  • the inventors have discovered that the effect on the shape of the silica nanoparticles can be influenced by the amount of water present in the reaction mixture in addition to the different speed of reaction of at least two organoalkoxysilanes.
  • the literature typically teaches use of an excess of water in the Stober process, excess water used with the mixture of at least two organoalkoxysilanes only leads to small deviations from the spherical shape. The inventors have discovered that more pronounced deviations are observed if less water is used for the hydrolysis reaction in the current process.
  • water of the catalyst solution is preferred to use as the sole source of water , such as 25-35% ammonia solution in water.
  • Water can be added to the reaction mixture if a catalyst solution used in the process does not contain or does not have enough water.
  • a water-miscible organic solvent is used in the process of the present invention.
  • Examples of the organic solvent include an alcohol, a ketone, an ether, a glycol, and an ester, with an alcohol being preferred. More particularly, alcohols such as methanol, ethanol, propanol, and butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol ethers such as propylene glycol monopropyl ether; glycols such as ethylene glycol, propylene glycol, and hexylene glycol; and esters such as methyl acetate, ethyl acetate, methyl lactate, and ethyl lactate are preferred. Among them, methanol or ethanol is more preferred, and ethanol is particularly preferred. These water-miscible organic solvents may be used alone or in a mixture of two or more.
  • the water-miscible organic solvent is preferably used in the reaction mixture in an amount of from about 25 to about 95% by weight of the reaction mixture total weight. In other embodiments, the water-miscible organic solvent is used from 40 wt.% to about 90 wt.%, or from about 50 wt.% to about 80 wt.% by weight of the reaction mixture.
  • At least one alkaline catalyst is used in the process of the present invention.
  • the alkaline catalyst is selected from the group consisting of ammonia (NH 3 ), ammonium hydroxide, an organic amine, an alkanolamine, a quaternary ammonium hydroxide compound, and combinations thereof.
  • Preferred alkaline catalysts include ammonia (NH 3 ) or at least one organic amine.
  • Suitable organic amines for use as the at least one alkaline catalyst include hexyl amine, 5-amino-2-methyl pentane, heptyl amine, octyl amine, nonyl amine, decyl amine, dipropyl amine, diisopropyl amine, dibutyl amine, diisobutyl amine, di-n- butyl amine, di-t-butyl amine, dipentyl amine, dihexyl amine, diheptyl amine, dioctyl amine, dinonyl amine, didecyl amine, amyl methyl amine, methyl isoamyl amine, tripropyl amine, tributyl amine, tripentyl amine, dimethyl ethyl amine, methyl diethyl amine, methyl dipropyl amine, N-ethylidene methyl amine, N-
  • alkanolamines include primary, secondary and tertiary alkanolamines having from 1 to 5 carbon atoms such as, for example, N- methylethanolamine (NMEA), monoethanolamine (MEA), N-methyl diethanolamine, diethanolamine, mono-, di- and triisopropanolamine, 2-(2-aminoethylamino) ethanol, 2- (2-aminoethoxy) ethanol, triethanolamine, and mixtures thereof.
  • NMEA N- methylethanolamine
  • MEA monoethanolamine
  • N-methyl diethanolamine diethanolamine
  • diethanolamine diethanolamine
  • mono- and triisopropanolamine 2-(2-aminoethylamino) ethanol
  • 2- (2-aminoethoxy) ethanol 2- (2-aminoethoxy) ethanol
  • triethanolamine triethanolamine
  • Suitable quaternary ammonium hydroxide compounds for use as the at least one alkaline catalyst include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, (2- hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (1- hydroxypropyl)trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide and benzyltrimethylammonium hydroxide, or mixtures thereof.
  • TMAH tetramethylammonium hydroxide
  • TBAH tetrabutylammonium hydroxide
  • the amount of the alkaline catalyst added to the reaction mixture may be appropriately adjusted so that the pH of the reaction mixture is maintained in the range of 7 to 14, preferably 10 to 14, and more preferably 12 to 14.
  • the alkaline catalyst can be added to the mixture of at least two organoalkoxysilanes and the water-miscible organic solvent; or can be added to the water-miscible organic solvent first and then add into the mixture of at least two organoalkoxysilanes to obtain a reaction mixture.
  • the alkaline catalyst is added to the mixture of at least two organoalkoxysilanes and the water-miscible organic solvent while stirring to obtain the reaction mixture.
  • the catalyst can be present as aqueous solution such as 25% - 35% solution of ammonia in water, so that water as a reactant is added at the same time like the catalyst.
  • the addition of the catalyst can be slow or all at once.
  • the catalyst is added quickly under vigorous stirring to a pre-heated silane/solvent mixture.
  • a typical reaction time is from 1 to 5 hours.
  • both silane/solvent mixture and the catalyst are heated. Still more preferably, both are heated to the same temperature prior to mixing. Exemplary temperatures include those in the range of from 30 °C to 70 °C, from 40 °C to 60 °C, and from 48 °C to 52 °C.
  • the process should be designed in a way to avoid the evaporation of volatile catalysts (such as NH 3 ) from the reaction mixture.
  • volatile catalysts such as NH 3
  • a continuous pipe/flow reactor or a batch reactor with a sufficiently long pipe can be used to ensure that the reaction proceeds to a desired extent (particle formation).
  • the excess water is added to achieve a ROR value of at least ⁇ 1.0, most preferably ⁇ 2.0. Due to the unique way of particle growth, the colloidal silica produced by the process of the present invention having a non-spherical, elongated, bent and branched structures can be obtained.
  • a second growth step can be performed.
  • the process of the present invention further comprises the step of adding at least an organoalkoxysilane and water and, optionally, more of the alkaline catalyst to the reaction mixture.
  • the optional second growth step is performed with only one organoalkoxysilane compound such as, for example, TEOS.
  • the addition rate for the second step is preferably drop-wise addition of the organoalkoxysilane to maintain the pH of the liquid mixture at 7, preferably, from 12 to 14.
  • the addition rate of the organoalkoxysilane for the optional second growth step is preferably 0.7 to 41 g of silica/hour/kg of the reaction mixture.
  • a next step of the process of the present invention comprises exchanging at least a portion of the water-soluble organic solvent for water once the non-spherical primary silica nanoparticles are formed to obtain a dispersion of the silica nanoparticles in water.
  • Such solvent exchange step can use any know process for exchanging organic solvent for water such as, for example, distillation or cross-flow filtration.
  • the solvent exchange step preferably is performed until as much of the organic solvent as possible is removed subject to any inherent limitation of the process employed.
  • the exchanging step comprises adding water in an amount to achieve a molar ratio of water and hydrolysable groups on the organoalkoxysilanes (ROR) of greater than or equal to 2.0.
  • the dispersion resulting after the solvent exchange step is concentrated by any suitable means to obtain a solid concentration of from 15 to 25% or more.
  • the process of the present invention may include other optional steps, such as chemically modifying the surface of the produced colloidal silica.
  • the typical silica surface is terminated (covered) with — OH groups under neutral or basic conditions.
  • the silica surface is hydrophilic and, thus, “wettable.” These groups activate the surface to a number of possible chemical or physioabsorbtion phenomena.
  • the Si — OH groups impart a weak acid effect which allows for the formation of salts and to exchange the proton (H + ) for various metals (similar to the ion exchange resins).
  • Si — O and Si — OH can also act as ligands for complexing Al, Fe, Cu, Sn and Ca.
  • the surface is very dipolar and so electrostatic charges can accumulate or be dissipated depending on the bulk solution's pH, ion concentration and charge. This accumulated surface charge can be measured as the Zeta potential.
  • the CMP liquid containing abrasive particles may need to undergo a pH adjustment, for example where a high zeta potential is attainable to retain colloidal stability. It is undesirable in an abrasive-containing liquid for the particles to settle out of the suspension. Electrical charges surrounding the interface between the particle and the liquid strongly influence the stability of the colloidal system.
  • the Zeta potential measures the potential of a particle's surface at its shear plane and provides a general measure of the stability of a colloidal system. To maintain a stable colloidal system, a high Zeta potential of either positive or negative charge is desired. The Zeta potential of the particular particle decreases to zero at the pH corresponding to its isoelectric point.
  • the pH of the system should differ from the pH at the isoelectric point.
  • the isoelectric point of a silica slurry is at a pH of 2; preferably, then, the silica slurry is maintained at an alkaline pH to enhance the colloidal stability.
  • Other variables which affect the colloidal stability of a particulate system include particle density, particle size, particle concentration, and chemical environment.
  • the optional step of chemically modifying the surface of the produced colloidal silica can include any surface modification to adjust the Zeta potential of the colloidal dispersion or to impart any other desired functionality to the surface of the colloidal silica.
  • the colloidal silica particles can be surface-modified using any suitable process as is known in the art. This includes modifying the surface of the colloidal silica by adding metal ions, boron, aluminum etc.
  • the optional modifying step also includes treatment with surface-modifying agents such as silanes, including amino-containing silanes, sulfur-containing silanes, carboxy-group containing silanes, phosphorous- containing silanes, alkyl silanes, and the like.
  • the step of modifying a surface of the non-spherical silica nanoparticles comprises replacing at least a portion of surface silanol groups with at least one selected from the group consisting of an organosilane, an organic polymer, an inorganic polymer, a surfactant, and an inorganic salt.
  • the step of modifying a surface of the non-spherical silica nanoparticles comprises replacing at least a portion of surface silanol groups with the organosilane selected from the group consisting of an amino-functional alkoxysilane, a cyanofunctional alkoxysilane, an alkyl- and aryl- functional alkoxysilane, a sulfursilane, and a phosphorsilane.
  • organosilane selected from the group consisting of an amino-functional alkoxysilane, a cyanofunctional alkoxysilane, an alkyl- and aryl- functional alkoxysilane, a sulfursilane, and a phosphorsilane.
  • sulfursilanes include mercaptopropyltriethoxysilane, mercaptopropyltrimethoxysilane, and bis[3-(triethoxysilyl)propyl]polysulfide (Reg.
  • phosphorsilanes include N- diphenylphosphoryl-3-aminopropyltriethoxysilane, 3-(trihydroxysilyl)propyl methylphosphonate (ammonium salt), and 2- (diethylphosphatoethyl)methyldiethoxysilane.
  • the pH of the dispersion is acidic. This may be accomplished by any means known to those skilled in the art such as, for example, by passing the colloidal silica dispersion through an ion exchange resin until present cations are exchanged by H + ions or by addition of a suitable acid. Such ion exchange can be performed either before or after the optional surface modification step.
  • Suitable particle stabilizing additives can be added to the dispersion. These include surfactant compounds. Suitable surfactant compounds include, for example, any of the numerous nonionic, anionic, cationic or amphoteric surfactants known to those skilled in the art. The surfactant compounds may be present in the slurry composition in a concentration of about 0 weight % to about 1 weight % and, when present, are preferably present in a concentration of about 0.001 weight % to about 0.1 weight % of the total weight of the slurry. [0095] Other compounds can be added to the dispersions prepared herein, depending on the particular end use. These include chelating agents, corrosion inhibitors, colloidal stabilizers, organic or inorganic salts, and biological agents such as bactericides, biocides and fungicides.
  • the silica nanoparticles produced herein mainly comprise non-spherical primary silica particles, i.e., they are elongated and/or bent and/or branched particles.
  • the non-spherical primary silica nanoparticles comprise about 75%, 85%, or greater of the silica nanoparticles produced according to the inventive process disclosed herein.
  • the yield is defined as the total weight of silica nanoparticles which can be produced by the total weight of the reaction mixture and is typically reported as weight% yield.
  • Typical Stober processes are very limited in their yield since attempts to achieve higher yields always lead to uncontrolled aggregation, precipitation or inhomogeneous size distributions. So, Stober processes are typically performed at yields of 1-3 % which means that most of the reaction mixture is solvent which needs to be removed in expensive downstream processes.
  • the described process can be done at yields ranging from 0.5 - 15%, preferably from 3% - 8% and most preferably from 5% to 7% yield, which is a huge advantage meaning that about only half the amount of solvent is needed compared to Stober processes known in the state of the art. So, in downstream processing also only half the amount of solvent has to be exchanged against water or removed.
  • the working examples in the application have shown the yields from 4.5-6.5%, or 5.5 to 6.5%.
  • the non-spherical primary silica particles might come into contact with each other and form some kind of bond like hydrogen-bridges or covalent bonds and aggregate to form secondary particles.
  • the silica secondary particles mostly are non- spherical, or have elongated, bent structure, and/or a branched structure.
  • the term “aspect ratio” refers to a ratio of the major axis to the minor axis of the particles.
  • the non-spherical primary silica nanoparticles produced according to the process disclosed herein have an average value of the aspect ratio of the particles (an average aspect ratio) observed in the above view is preferably 1 .5 or more and, more preferable, less than 5. If the average aspect ratio exceeds 5, handling thereof will be difficult due to the increase in viscosity etc., and gelation may occur.
  • the non-spherical primary silica nanoparticles can have an mean particle size of about 15 nm to 200 nm, about 20 nm to about 200 nm, about 20 nm to about 150 nm, about 20 nm to about 120 nm, about 20 nm to about 110 nm, about 20 nm to about 110 nm, about 30 nm to about 110 nm, about 30 nm to about 100 nm, about 30 nm to about 90 nm, about 30 nm to about 80 nm, or about 40 nm to 70 nm.
  • the non-spherical primary silica nanoparticles can have an mean particle size of about ⁇ 10nm, about ⁇ 15 nm, and about 3 ⁇ 43 ⁇ 4 200 nm, about 3 ⁇ 43 ⁇ 4 150 nm, about 3 ⁇ 43 ⁇ 4 120 nm, about 3 ⁇ 43 ⁇ 4100 nm, about 3 ⁇ 43 ⁇ 4 90 nm, about 3 ⁇ 43 ⁇ 4 80 nm, or about 3 ⁇ 43 ⁇ 4 70 nm.
  • the non-spherical primary silica nanoparticles can have an mean particle size bounded by any two of the aforementioned endpoints.
  • the non-spherical silica secondary nanoparticles can have any suitable mean particle size.
  • the non-spherical silica secondary nanoparticles can have an mean particle size of about 15 nm to 600 nm, about 20 nm to 600 nm, about 25 nm to 550 nm, about 30 nm to 500nm, about 35 nm to 450 nm, about 40 nm to 400 nm, about 45 nm to 350 nm, about 50 nm to 300 nm, or about 50 nm to 200 nm.
  • the non-spherical silica secondary nanoparticles can have an mean particle size of about ⁇ 15 nm and 3 ⁇ 43 ⁇ 4 600 nm, about 3 ⁇ 43 ⁇ 4 500 nm, about 3 ⁇ 43 ⁇ 4 400 nm, about 3 ⁇ 43 ⁇ 4 300 nm, or about 3 ⁇ 43 ⁇ 4 200 nm.
  • the silica nanoparticles can have an mean particle size bounded by any two of the aforementioned endpoints. It is preferred that the inventive non-spherical primary particles are not or only to a small extend aggregated to form secondary particles.
  • the present invention provides non-spherical primary silica nanoparticles prepared by the process disclosed above.
  • the inventive non-spherical primary silica nanoparticles have a bent and/or branched structure, and thus a large aspect ratio. Since the inventive elongated/bent/aggregated primary silica particles are superimposed over or entangled with one another, they exhibit excellent coating properties, and can therefore improve the coating properties when used as a vehicle for aqueous coating compositions.
  • the non-spherical primary silica nanoparticles produced herein are an excellent abrasive for use in CMP compositions as they exhibit high removal rates and high efficiency as compared to spherically-shaped particles. Accordingly, in another embodiment, provided herein is a CMP composition comprising the non-spherical primary silica nanoparticles produced according to the process disclosed herein.
  • the contact resistance between the polishing material and a surface to be polished can be adjusted to thereby improve the polishing rate.
  • Example 1 Synthesis of elongated particles (5% TMOS 95% TEOS, ROR 0.75)
  • FIGS. 1 and 2 are SEM micrographs showing the non-spherical primary silica nanoparticles produced by Example 2.
  • FIGS. 3 and 4 are SEM micrographs showing the non-spherical primary silica nanoparticles produced by Example 3.
  • Example 4 (60% TEOS, 40% TPOS, ROR 0.75)
  • FIGS. 5 and 6 are SEM micrographs showing the non-spherical primary silica nanoparticles produced by Example 4.
  • nanoparticle dispersion from example 2 was stirred and 700 g ion exchanger Amberlite IRN-150 was added. Stirring was continued for 1 hour before the ion exchanger was filtered off. pH was measured with a pH electrode to be 4.3. HNO3 (1%) was added slowly until the pH of the dispersion was 2.0.
  • Example 6 Surface modification, zeta-potential adjustment and solvent transfer
  • the dispersion was then transferred to a rotary evaporator and alcohols were removed stepwise and replaced by adding water until the dispersion reached a solid content in water of 21.5 wt.%.
  • the particles had a mean particle size of 90.5 nm, PDI of 0.058 by DLS, and zetapotential: 40.3 mV, at pH 2.2.
  • Example 7 Synthesis of Elongated Particles (90%TEOS, 10%TMOS, ROR 0.75)
  • the reaction mixture was kept at 60°C for 12 h then particle size was measured by DLS.
  • the particles had a mean particles size of 77.7 nm, and PDI of 0.054.
  • the particles had a Mean particle size of 47.4 nm, and PDI of 0.025.
  • the very low PDI is an indicator that the particles are hardly elongated or non- spherical and therefore are not favorable regarding the requirement profile.
  • Example 8 Nitrogen Level (or Nitrogen Content )

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silicon Compounds (AREA)
  • Silicon Polymers (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
EP22792670.6A 2021-04-21 2022-04-14 Non-spherical primary silica nanoparticles and the use therefor Pending EP4326678A1 (en)

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